Fugicidal composition comprising 5-chloro-salicylic acid amylamide



United States Patent Office 2,861,916 Pa fented Nov. 25, 1958 12,861,916 FUNGICIDAL COMPOSITION COMPRISING S-CHLORO-SALICYLIC ACIDAMYLAMIDE Ernst Model, Basel, and Jakob Bindler, Riehen, near Basel,Switzerland, assignors to J. R. Geigy A-.-G., Basel, Switzerland, :1Swiss firm No Drawing. Application July 9, 1956 Serial No. 596,445Claims priority, application Switzerland July 22, 1955 3 Claims. (Cl.167-31) The invention concerns fungicidal agents, their use for theprotection of organic material and possibly also of the skin of man andanimals from attack by fungi and/ or injury due to rot as the case maybe, as well'as, as industrial product, the organic material protectedagainst attack by fungi and/or rot with the aid of these agents.

The use of salicylic acid phenylamides as well as derivatives of thiscompound halogenated in the anilide radical as fungicidal agents, e. g.in textile printing pastes, is known.

It has now been found that amides of salicylic acid halogen substitutedin the benzene ring which are derived from aliphatic primary amines withhydrocarbon radicals having 5 carbon atoms have a stronger fungicidalaction than the comparable aromatic amides. They are excellentlysuitable therefore as active ingredients in the production of fungicidalagents and for the protection of organic material from attack by fungiand/or damage due to rot. This superior fungicidal action isparticularly apparent in the protection of cotton against damage byfungi.

The active ingredients usable according to the present invention areobtained by methods known per se either by amidation of thecorresponding halogen substituted salicylic acid ester of lower alcoholswith the aliphatic primary amines having alkyl radicals of 5 carbonatoms or by reacting halogen substituted salicylic acid halides withexcess aliphatic primary amines having 5 carbon atoms. They can bepurified by distillation, advantageously under reduced pressure, and arewhite, well crystallised compounds which dissolve only a little in waterbut easily in aqueous alkalies as well as in the usual organic solvents.This good solubility and the relatively good stability in alkalinesolution enables the active ingredients to be used in textile treatmentliquors which can contain for example, apart from soap in the usualmeaning of the word and detergents, also the inorganic salts usual inwashing and cleansing liquors such as Glaubers salt, pyroorpoly-phosphates, sodium silicates etc., or they can be used in the usualorganic solvents such as are used for the dry cleaning of textiles orfor the production of so-called sprays. They can also be mixed withsoaps or synthetic washing agents which then pro duce washing liquorswhich give to the organic material washed therein, in particularcellulose textiles, good protection from attack by fungi, rot or mildewspots. Another type of use is the incorporation of salts and emulsionsof the active ingredients to produce antiseptic soaps and pastes forhuman and veterinary purposes. The active ingredients can also be mixedinto printing thickeners consisting of starch or cellulose derivatives,and also into lacquers and paints consisting chiefly of casein.

All these compositions characterised by a content of active ingredientsof the type described are regarded as falling Within the scope of theprocess according to the present invention.

The fungicidal active ingredients according to the present invention areapplied to the organic material to be protected either by simple mixingor working in of solutions, emulsions or suspensions of the activeingredients or by spraying or impregnating with solutions, emulsionsingredients The solutions of the activeingredient, contents of from 0.5to 5 g. per

litre of treatment liquor suflice for an effective protection of thesprayed, impregnated or washed material against attack by fungi, rot orformation of mildew spots. Organic material having a content of 0.05 to0.5% active ingredient, calculated on its own weight, is generallyeffectively and relatively lastingly protected against 'attack by fungi.V g n H Chiefiy cellulose in' textile form is meant by organic materialto be protected. However, also other organic substances which tend tomould or for can be protected, for example, pape'r, leather, vegetableor animal mucilage and gels, polyvinyl permanent finishes etc.

The following examples serve to illustrate the invention. Where nototherwise'stated, partsare given aspar'ts by weight. The temperaturesare in degrees centigrade. The relationship of parts by weight to partsby volume is as that of kilogrammes to litres.

EXAMPLE 1 Calico is dipped for30 seconds in an alcoholic S0111; tionwhich contains 5 g. of 3,5-dichlorosalicylic acid-namylamide per litre.its weight and drying, the material treated is protected against mildewspots and rot.

(a) Mildew spot test Rings of material of 9 cm. diameter are laid on anagar nutrient medium in petri dishes and inoculated With a suspension ofthe mixture of spores of Penicillium expansum, Stochybotrys atm andAspergillus niger which contains 40,000 germs per ccm. The closed petridishes are left for 10 days at 28 and then the number of fungi coloniesis counted.

( b) Rotting test Rings of fabric of 3.8 cm. diameter are laid on anagar nutrient medium in petri dishes which has been inoculated with 0.5ccm. of a suspension of the spores of Chaetomium globosum which containsabout 700,000 germs per ccm. The dishes are left for 10 days at 28, thedevelopment of the germs is then interrupted with an alcoholic thymolsolution, the rings of material are rinsed and dried. The material isthen tested in the spot tester according to R. Burgess (Microorganismsand Textiles: The Journal of Applied Bacteriology, 17, 241 (1954)) tosee if the strength of the material has been reduced.

(0) Soil burial test Rings of fabric of 3.8 cm. diameter are buried for14 days in an earth mixture of a moisture content of 30% and atemperature of 28 and consisting of 50% compost, 30% cow dung and 20%sand. The fabric is then rinsed and dried, and then tested in the spottester according to Burgess to see if its strength has been reduced.

In the rotting and soil burial test, the value given is the average of10 tests. The strength is given in percent of that of the originalmaterial.

The results of these tests can be seen from the table.

EXAMPLE 2 Calico is dipped in a 0.1% alcoholic solution of 5-chlorosalicylic acid isoamylamide for 30 seconds (liquor ratio 1:20),squeezed out to of its weight and dried in a drying oven. The materialso treated is protected against mildew spots and rot. On testing thetreated samples by the methods given in Example 1, the results given inthe table were obtained.

After squeezing out to 100% of i TABLE g. active mildew spot test-No. ofRotting testsubstance fungi colonies Chaelomz'um Soil burial Example perlitre globosum treatment strength strength liquor Asp. n. Stach. a. Pen.e.

Percent Percent 1 0.5 0 0 2 1 0 0 0 100 97 untreated fabric..- 0 11 12What we claim is: References Cited in the file of this patent 1. Afungicidal composition comprising as active in- 15 UNITED STATES PATENTSgredient a compound corresponding to the formula: 1 873 365 Fargher g 231932 OH 235831425 Hawley Jan. 22: 1952 Geo-armour OTHER REFERENCES 20Chem. Abst., vol. 46, p. 104301: 1952.

C1 U. S. Dept. of Agri., Agri. Handbook No. 69, 1954, and a fungicidaladjuvant as a carrier therefor. p. 307, Chem. Eval. as Insect. and Rep.at Orlando, Fla. 2. A fungicidal composition comprising as active in- J.Pharm. and Exp. Ther. Sch. of Med. and Coll. Phan, gredientS-chloro-salicylic acid-n-amylarnide and a fun- U. of Cal., vol. 108,pp. 450-460, 1953. gicidal adjuvant as a carrier therefor. 25 J. ofEcon. Ent., vol. 40, 1947, pp. 736-741.

3. A fungicidal composition comprising as active in- U. S. Dept. Agri.,Agri. Res. Adm, Bur. of But. and

gredient 5-chlorosalicylic acid-isoamylamide and a fun- PlantQuarantine, Questen and Gertler, E-778, June 1949. gicidal adjuvant as acarrier therefor.

1. A FUNGICIDAL COMPOSITION COMPRISING AS ACTIVE INGREDIENT A COMPOUNDCORRESPONDING TO THE FORMULA: